JP2015196702A - Azeotropic or azeotropic-like composition containing 1-chloro-3,3,3-trifluoro propene and 1,1,1,3,3-pentafluoro propane - Google Patents

Azeotropic or azeotropic-like composition containing 1-chloro-3,3,3-trifluoro propene and 1,1,1,3,3-pentafluoro propane Download PDF

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JP2015196702A
JP2015196702A JP2014073688A JP2014073688A JP2015196702A JP 2015196702 A JP2015196702 A JP 2015196702A JP 2014073688 A JP2014073688 A JP 2014073688A JP 2014073688 A JP2014073688 A JP 2014073688A JP 2015196702 A JP2015196702 A JP 2015196702A
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refrigerant
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hfc245fa
hcfo1233zd
refrigerator
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JP5983671B2 (en
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土屋　立美
Tatsumi Tsuchiya
立美 土屋
柴沼　俊
Takashi Shibanuma
俊 柴沼
山田　康夫
Yasuo Yamada
康夫 山田
眸 黒木
Hitomi Kuroki
眸 黒木
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Daikin Industries Ltd
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Priority to EP15772888.2A priority patent/EP3127985B1/en
Priority to US15/129,906 priority patent/US10253231B2/en
Priority to PCT/JP2015/060240 priority patent/WO2015152286A1/en
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Abstract

PROBLEM TO BE SOLVED: To provide a novel refrigerant mixture which can substitute for HCFC123, is a low ODP (Ozone-Deleting Potential) and low GWP (Global Warming Potential) refrigerant, has COP equivalent to that of HCFC123 and has refrigeration capacity and gas density higher than those of a single refrigerants such as HCFO1233zd(E), HFC245fa which are considered as alternative refrigerants for HCFC123.SOLUTION: There is provided a composition containing a refrigerant, and the refrigerant contains HCFO1233zd(E) and HFC245fa with a mass ratio of HCFO1233zd(E) to HFC245fa of 18:82 to 49:51.

Description

本発明は、トランス-1-クロロ-3,3,3-トリフルオロプロペン（本明細書において、「HCFO1233zd(E)」と表記することがある。）及び1,1,1,3,3-ペンタフルオロプロパン（本明細書において、「HFC245fa」と表記することがある。）を含有する共沸乃至共沸様組成物に関する。   The present invention relates to trans-1-chloro-3,3,3-trifluoropropene (in this specification, sometimes referred to as “HCFO1233zd (E)”) and 1,1,1,3,3- The present invention relates to an azeotropic or azeotrope-like composition containing pentafluoropropane (sometimes referred to as “HFC245fa” in this specification).

現在、大型チラー冷凍機、特にターボ冷凍機用の低圧冷媒として、2,2-ジクロロ-1,1,1-トリフルオロエタン（本明細書において、「HCFC123」と表記することがある。）が用いられている。   Currently, 2,2-dichloro-1,1,1-trifluoroethane (sometimes referred to as “HCFC123” in this specification) is a low-pressure refrigerant for large chiller refrigerators, particularly turbo refrigerators. It is used.

しかしながら、HCFC123は分子中に塩素を含むハイドロクロロフルオロカーボン（HCFC）であり、オゾン層保護のため、段階的に使用が禁止されつつある。   However, HCFC123 is a hydrochlorofluorocarbon (HCFC) containing chlorine in the molecule, and its use is being banned step by step to protect the ozone layer.

このため、分子中に塩素を含まずオゾン層破壊係数（ODP： Ozone-Depleting Potential）がゼロであるハイドロフルオロカーボン（HFC）を利用した新しい冷媒への代替化が進められてきた。しかしながら、HFC冷媒は非常に安定であるため地球温暖化係数（Global Warming Potential: GWP）が高く、近年は欧州でのF-gas規制を初め地球環境保護のために使用の削減が進められている。そこで、GWPの低い冷媒としてHFO（ハイドロフルオロオレフィン）、及び塩素を含有しているが2重結合を有するため大気寿命が短く、GWPだけでなくODPも非常に低いHCFO（ハイドロクロロフルオロオレフィン）冷媒が開発されている。   For this reason, replacement with new refrigerants using hydrofluorocarbon (HFC), which does not contain chlorine in the molecule and has an Ozone-Depleting Potential (ODP) of zero, has been promoted. However, HFC refrigerants are very stable and have a high global warming potential (Global Warming Potential: GWP). In recent years, the use of HFC refrigerants has been promoted to protect the global environment, including F-gas regulations in Europe. . Therefore, HCFO (hydrochlorofluoroolefin) refrigerant that contains HFO (hydrofluoroolefin) and chlorine as a refrigerant with low GWP but has a double bond and has a short atmospheric life, and not only GWP but also ODP is very low. Has been developed.

例えば、HCFO1233zd(E)がHCFC123の代替冷媒として使用できることが提案されており、任意で加えてもよい冷媒としてHFC245faが示されているが混合割合は示されていない。（特許文献１）。また、熱移動媒体の組成物として少なくとも50重量%のHCFO1233zd(E)を含むHCFC123代替冷媒が提案されている（特許文献２）。   For example, it has been proposed that HCFO1233zd (E) can be used as an alternative refrigerant for HCFC123, and HFC245fa is shown as an optional refrigerant, but the mixing ratio is not shown. (Patent Document 1). Further, an HCFC123 alternative refrigerant containing at least 50% by weight of HCFO1233zd (E) as a composition of the heat transfer medium has been proposed (Patent Document 2).

ＵＳ２０１０／０３２６０９５Ａ１US2010 / 0326095A1 国際公開第ＷＯ２０１０／０７７８９８号International Publication No. WO2010 / 077788

本発明は、HCFC123を代替することができ、低ODPかつ低GWP冷媒であって、HCFC123と同等のCOPを有し、かつ冷凍能力及びガス密度が、HCFC123の代替冷媒として考えられているHCFO1233zd(E)、HFC245fa等の単一冷媒よりも高い、混合冷媒を提供することを課題とする。   The present invention can replace HCFC123, is a low ODP and low GWP refrigerant, has a COP equivalent to HCFC123, and has a refrigeration capacity and gas density considered as an alternative refrigerant for HCFC1233zd ( E) It is an object to provide a mixed refrigerant that is higher than a single refrigerant such as HFC245fa.

本発明者らは、上記課題に鑑みて鋭意研究を重ねた結果、HCFO冷媒及びHFC冷媒をそれぞれ単独で使用する場合よりも、それらを任意の割合で混合させた組成物の冷凍能力及びガス密度がより優れている事を見出した。かかる知見に基づき本発明者らは、さらに検討を重ね、HCFO冷媒の中でもGWPが比較的低いHCFO1233zd(E)と、HFC245faを組み合わせて用いることを想到するに至った。さらなる試行錯誤の結果、本発明者らは、HCFO1233zd(E)及びHFC245faを特定の比率で含有する共沸乃至共沸様組成物が、従来のHCFC123よりも低ODP、低GWPかつ優れた冷凍能力及びガス密度を備えており、上記課題を解決できることを見出した。   As a result of intensive studies in view of the above problems, the present inventors have determined that the refrigeration capacity and gas density of a composition in which they are mixed at an arbitrary ratio, compared with the case where HCFO refrigerant and HFC refrigerant are used alone, respectively. Found out that it was better. Based on such knowledge, the present inventors have further studied and came up with the idea that HCFO1233zd (E) having a relatively low GWP among HCFO refrigerants and HFC245fa are used in combination. As a result of further trial and error, the present inventors found that an azeotropic or azeotrope-like composition containing HCFO1233zd (E) and HFC245fa in a specific ratio has a lower ODP, lower GWP, and superior refrigeration capacity than the conventional HCFC123. And having a gas density, the present inventors have found that the above problems can be solved.

本発明は、かかる知見に基づきさらに研究を重ねた結果完成されたものである。本発明は、以下の実施態様を含む。   The present invention has been completed as a result of further research based on such knowledge. The present invention includes the following embodiments.

項１． 冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比が、18:82〜49:51である、
組成物。 Item 1. A composition containing a refrigerant,
The refrigerant contains HCFO1233zd (E) and HFC245fa, and
The mass ratio of HCFO1233zd (E) to HFC245fa is 18:82 to 49:51,
Composition.

項２． 冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比が、29:71〜38:62である、
組成物。 Item 2. A composition containing a refrigerant,
The refrigerant contains HCFO1233zd (E) and HFC245fa, and
The mass ratio of HCFO1233zd (E) to HFC245fa is 29:71 to 38:62,
Composition.

項３． 冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有する共沸乃至共沸様組成物である、
組成物。 Item 3. A composition containing a refrigerant,
The refrigerant is an azeotropic or azeotrope-like composition containing HCFO1233zd (E) and HFC245fa,
Composition.

項４． さらに冷凍機油を含有する、項１〜３のいずれかに記載の組成物。   Item 4. Item 4. The composition according to any one of Items 1 to 3, further comprising refrigerating machine oil.

項５． 前記冷凍機油が、ポリアルキレングリコール（PAG）、ポリオールエステル（POE）及びポリビニルエーテル（PVE）からなる群より選択される少なくとも一種の冷凍機油である、項４に記載の組成物。   Item 5. Item 5. The composition according to Item 4, wherein the refrigerating machine oil is at least one refrigerating machine oil selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

項６． 大型チラー冷凍機用冷媒として用いられる、項１〜５のいずれかに記載の組成物。   Item 6. Item 6. The composition according to any one of Items 1 to 5, which is used as a refrigerant for a large chiller refrigerator.

項７． 2,2-ジクロロ-1,1,1-トリフルオロエタン（HCFC123）の代替冷媒として用いられる、項１〜６のいずれかに記載の組成物。   Item 7. Item 7. The composition according to any one of Items 1 to 6, which is used as an alternative refrigerant for 2,2-dichloro-1,1,1-trifluoroethane (HCFC123).

項８． 項１〜５のいずれかに記載の組成物の、大型チラー冷凍機用の冷媒としての使用。   Item 8. Use of the composition according to any one of Items 1 to 5 as a refrigerant for a large chiller refrigerator.

項９． 項１〜５のいずれかに記載の組成物の、HCFC123の代替冷媒としての使用。   Item 9. Item 6. Use of the composition according to any one of Items 1 to 5 as an alternative refrigerant for HCFC123.

項１０． 項１〜５のいずれかに記載の組成物を用いて冷凍サイクルを運転する工程を含む、冷凍方法。   Item 10. Item 6. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of Items 1 to 5.

項１１． 項１０に記載の工程を含有する、大型チラー冷凍機の運転方法。   Item 11. Item 11. A method for operating a large chiller refrigerator, comprising the step according to item 10.

項１２． 項１〜５のいずれかに記載の組成物を含む冷凍機。   Item 12. Item 6. A refrigerator including the composition according to any one of Items 1 to 5.

項１３． 大型チラー冷凍機である、項１２に記載の冷凍機。   Item 13. Item 13. The refrigerator according to Item 12, which is a large chiller refrigerator.

項１４． HCFO1233zd(E)及びHFC245faを含有する組成物の製造方法であって、
HCFO1233zd(E)のHFC245faに対する質量比が18:82〜49:51となるように、少なくともHCFO1233zd(E)及びHFC245faを混合する工程
を含む製造方法。 Item 14. A method for producing a composition comprising HCFO1233zd (E) and HFC245fa,
A production method comprising a step of mixing at least HCFO1233zd (E) and HFC245fa so that a mass ratio of HCFO1233zd (E) to HFC245fa is 18:82 to 49:51.

本発明の冷媒組成物は、大型チラー冷凍機（ターボ冷凍機等）用冷媒に適しており、共沸乃至共沸様を示すため気相及び液相の組成変化がなく単一物として扱うことができ、かつ冷媒性能の指標である冷凍能力及びガス密度が高い。   The refrigerant composition of the present invention is suitable as a refrigerant for large chiller refrigerators (turbo refrigerators, etc.) and exhibits azeotropic or azeotropic behavior, so that it is not changed in the composition of the gas phase and liquid phase and should be handled as a single product. And the refrigerating capacity and gas density, which are indicators of refrigerant performance, are high.

１．組成物
本発明の組成物は、
冷媒を含有する組成物であって、冷凍能力及びガス密度の点で好ましくは
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比、すなわち、HCFO1233zd(E):HFC245faが、18:82〜49:51である組成物である。 1. Composition The composition of the present invention comprises:
A composition containing a refrigerant, preferably in terms of refrigeration capacity and gas density, the refrigerant contains HCFO1233zd (E) and HFC245fa, and
A composition in which the mass ratio of HCFO1233zd (E) to HFC245fa, ie, HCFO1233zd (E): HFC245fa is 18:82 to 49:51.

また、本発明の組成物は、冷凍能力及びガス密度の点で、更に好ましくは
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比が、29:71〜38:62である、
組成物である。 Further, the composition of the present invention is more preferably a refrigerant containing HCFO1233zd (E) and HFC245fa in terms of refrigeration capacity and gas density, and
The mass ratio of HCFO1233zd (E) to HFC245fa is 29:71 to 38:62,
It is a composition.

HCFO1233zd(E)及びHFC245faのみからなる二成分混合冷媒は、0〜100℃の温度範囲においてHCFO1233zd(E)／HFC245fa＝20.5〜38.9／61.1〜79.5mass%の組成範囲で最低共沸の共沸組成物となる。   The two-component mixed refrigerant consisting only of HCFO1233zd (E) and HFC245fa has the lowest azeotropic composition in the composition range of HCFO1233zd (E) /HFC245fa=20.5-38.9/61.1-79.5 mass% in the temperature range of 0-100 ° C. It becomes a thing.

この最低共沸組成物は、HCFO1233zd(E)及びHFC245faのみからなる二成分混合冷媒の組成範囲において、最も高い冷凍能力を示し、その冷凍能力はHFC245fa単独よりも高い。   This lowest azeotropic composition exhibits the highest refrigeration capacity in the composition range of the two-component mixed refrigerant consisting only of HCFO1233zd (E) and HFC245fa, and the refrigeration capacity is higher than that of HFC245fa alone.

18〜49mass%のHCFO1233zd(E)及び51〜82mass%のHFC245faのみからなる二成分混合冷媒は、共沸様となるため、HCFO1233zd(E)及びHFC245faのみからなる二成分混合冷媒の中で、比較的高い冷凍能力及び大きいガス密度を示す。具体的には、冷凍能力はHFC245fa単独よりも少なくとも4%高く、ガス密度は少なくとも5%大きい。   Since the two-component mixed refrigerant consisting of only 18-49 mass% HCFO1233zd (E) and 51-82 mass% HFC245fa becomes azeotropic, it is compared among the two-component mixed refrigerant consisting only of HCFO1233zd (E) and HFC245fa. High refrigeration capacity and high gas density. Specifically, the refrigeration capacity is at least 4% higher than the HFC245fa alone and the gas density is at least 5% higher.

29〜38mass%のHCFO1233zd(E)及び62〜71mass%のHFC245faのみからなる二成分混合冷媒は、共沸様となるため、HCFO1233zd(E)及びHFC245faのみからなる二成分混合冷媒の中で、比較的高い冷凍能力及び大きいガス密度を示す。具体的には、HFC245fa単独よりも少なくとも5%高く、ガス密度は少なくとも7%大きい。   Since the two-component mixed refrigerant consisting only of 29-38 mass% HCFO1233zd (E) and 62-71 mass% HFC245fa becomes azeotropic, it is compared among the two-component mixed refrigerant consisting only of HCFO1233zd (E) and HFC245fa. High refrigeration capacity and high gas density. Specifically, the gas density is at least 7% higher than HFC245fa alone and at least 7% higher.

本発明の組成物は、冷媒として、HCFO1233zd(E)及びHFC245faを含有する（comprising）。本発明の組成物は、本発明の主要な効果を妨げない限り、冷媒として、HCFO1233zd(E)及びHFC245faとは別の冷媒を含んでいてもよい。また、本発明の組成物は、本発明の主要な効果を妨げない限り、さらに他の成分を含んでいてもよい。   The composition of the present invention contains HCFO1233zd (E) and HFC245fa as refrigerants (comprising). The composition of the present invention may contain a refrigerant other than HCFO1233zd (E) and HFC245fa as a refrigerant as long as the main effects of the present invention are not hindered. Moreover, the composition of this invention may contain the other component, unless the main effect of this invention is prevented.

本発明の組成物に含まれる、HCFO1233zd(E)及びHFC245faとは別の成分としては、特に限定されないが、炭素数４〜５のハイドロカーボン化合物、並びに炭素数３の水素含有ハロゲン化アルカン、アルケン及びアルキン等が挙げられる。   Although it does not specifically limit as a component different from HCFO1233zd (E) and HFC245fa contained in the composition of this invention, A C4-C5 hydrocarbon compound and a C3-hydrogen-containing halogenated alkane, alkene And alkyne.

本発明の組成物には、各冷媒化合物のオリゴマーが含まれていてもよい。そのようなオリゴマーとしては、特に限定されないが、例えば、HCFO-1233zd（E）の２〜４量体のオリゴマー等が挙げられる。   The composition of the present invention may contain an oligomer of each refrigerant compound. Such an oligomer is not particularly limited, and examples thereof include a dimer to tetramer oligomer of HCFO-1233zd (E).

以上説明したHCFO1233zd(E)及びHFC245faとは別の成分は、単なる不純物として含まれていてもよく、冷媒特性を向上させるために積極的に添加されたものであってもよい。また、これらの別の成分は、冷凍機の運転中に冷媒が変化したものであってもよい。   Components other than HCFO1233zd (E) and HFC245fa described above may be included as simple impurities, or may be positively added to improve refrigerant characteristics. These other components may be those in which the refrigerant has changed during operation of the refrigerator.

HCFO1233zd(E)及びHFC245faとは別の成分である、炭素数４〜５のハイドロカーボン化合物は、飽和又は不飽和であってもよく、分枝型又は直鎖型であってもよい。特に限定されないが、例えば、n-ブタン、1-ブテン、2-ブテン、n-ペンタン、イソペンタン、neo-ペンタン、2-メチル-1-ブテン及び3-メチル-1-ブテン等が挙げられる。   The hydrocarbon compound having 4 to 5 carbon atoms, which is a component different from HCFO1233zd (E) and HFC245fa, may be saturated or unsaturated, and may be branched or linear. Although not particularly limited, examples thereof include n-butane, 1-butene, 2-butene, n-pentane, isopentane, neo-pentane, 2-methyl-1-butene, and 3-methyl-1-butene.

HCFO1233zd(E)及びHFC245faとは別の成分である、炭素数３の水素含有ハロゲン化アルカンとしては、特に限定されないが、例えばHFC-245eb、HFC-236cb、HFC-236ea及びHFC-236fa等が挙げられる。   The hydrogen-containing halogenated alkane having 3 carbon atoms, which is a component different from HCFO1233zd (E) and HFC245fa, is not particularly limited, and examples thereof include HFC-245eb, HFC-236cb, HFC-236ea, and HFC-236fa. It is done.

HCFO1233zd(E)及びHFC245faとは別の成分である、水素含有ハロゲン化アルケンとしては、特に限定されないが、例えば1,2,3,3,-ペンタフルオロプロペン（E及びZ体）2,3,3,3-テトラフルオロプロペン、1,3,3,3-テトラフルオロプロペン（E及びZ体）、2-ブロモ-1,3,3,3-テトラフルオロプロペン（E又はZ体）、1-ブロモ-2,3,3,3-テトラフルオロプロペン（E又はZ体）、2-ブロモ-3,3,3-トリフルオロプロペン、1-ブロモ-1,1,3,3,-テトラフルオロプロペン、1-ブロモ-3,3,3-トリフルオロプロペン（E及びZ体）、3-ブロモ-1,3,3−トリフルオロプロペン（E及びZ体）、3-ブロモ-3,3-ジフルオロプロペン、2-クロロ-1,3,3,3-テトラフルオロプロペン（E又はZ体）、1-クロロ-2,3,3,3-テトラフルオロプロペン（E又はZ体）、2-クロロ-3,3,3-トリフルオロプロペン、3-クロロ-1,1,3,3,-テトラフルオロプロペン、1-クロロ-3,3,3-トリフルオロプロペン（Z体）、3-クロロ-1,3,3−トリフルオロプロペン（E及びZ体）及び3-クロロ-3,3-ジフルオロプロペン等が挙げられる。   The hydrogen-containing halogenated alkene, which is a component different from HCFO1233zd (E) and HFC245fa, is not particularly limited. For example, 1,2,3,3, -pentafluoropropene (E and Z forms) 2,3, 3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene (E and Z form), 2-bromo-1,3,3,3-tetrafluoropropene (E or Z form), 1- Bromo-2,3,3,3-tetrafluoropropene (E or Z form), 2-bromo-3,3,3-trifluoropropene, 1-bromo-1,1,3,3-tetrafluoropropene 1-bromo-3,3,3-trifluoropropene (E and Z forms), 3-bromo-1,3,3-trifluoropropene (E and Z forms), 3-bromo-3,3-difluoro Propene, 2-chloro-1,3,3,3-tetrafluoropropene (E or Z form), 1-chloro-2,3,3,3-tetrafluoropropene (E or Z form), 2-chloro- 3,3,3-trifluoropropene, 3-chloro-1,1,3,3, -tetrafluoropropene 1-chloro-3,3,3-trifluoropropene (Z form), 3-chloro-1,3,3-trifluoropropene (E and Z form) and 3-chloro-3,3-difluoropropene Etc.

HCFO1233zd(E)及びHFC245faとは別の成分である、炭素数３の水素含有ハロゲン化アルキンとしては、特に限定されないが、例えば3,3,3-トリフルオロプロピンなどが挙げられる。   The hydrogen-containing halogenated alkyne having 3 carbon atoms, which is a component different from HCFO1233zd (E) and HFC245fa, is not particularly limited, and examples thereof include 3,3,3-trifluoropropyne.

HCFO1233zd(E)及びHFC245faとは別の成分の種類、及び冷媒全体に占める割合は、本発明の主要な効果を妨げない範囲内において、適宜選択及び設定することができる。別の成分の種類にもより、特に限定されないが、別の成分の総量が冷媒全体に占める割合が、0mass%〜10mass%であれば好ましく、0mass%〜5mass%であればより好ましい。   The types of components other than HCFO1233zd (E) and HFC245fa, and the proportion of the total refrigerant can be appropriately selected and set within a range that does not hinder the main effects of the present invention. Although it does not specifically limit by the kind of another component, It is preferable if the ratio for which the total amount of another component occupies the whole refrigerant | coolant is 0 mass%-10 mass%, and it is more preferable if it is 0 mass%-5 mass%.

本発明の組成物は、冷媒が、HCFO1233zd(E)及びHFC245faのみからなる（consisting of）もの（すなわち、二成分混合冷媒）であってもよい。   In the composition of the present invention, the refrigerant may consist of only HCFO1233zd (E) and HFC245fa (that is, a two-component mixed refrigerant).

本発明の組成物は、特に必須ではないが、さらに冷凍機油を含有していてもよい。この場合、本発明の組成物は、冷媒に加えてさらに少なくとも冷凍機油を含有する。   The composition of the present invention is not particularly essential, but may further contain refrigerating machine oil. In this case, the composition of the present invention further contains at least a refrigerating machine oil in addition to the refrigerant.

本発明の組成物は、冷凍機油として、特に限定されないが、一般に用いられる冷凍機油の中から適宜選択することができる。その際には、必要に応じて、冷媒との相溶性（miscibility）及び冷媒の安定性等を向上する作用等の点でより優れている冷凍機油を適宜選択してもよい。特に限定されないが、冷媒の安定性は、一般的に用いられる手法で評価することができ、そのような手法の一例として、ASHRE標準97-2007にしたがって遊離フッ素イオンの量を指標として評価する方法等が挙げられる。その他にも、全酸価（total acid number）を指標として評価する方法等も挙げられる。この方法は、例えば、ASTM D 974-06にしたがって行うことができる。   The composition of the present invention is not particularly limited as the refrigerating machine oil, but can be appropriately selected from commonly used refrigerating machine oils. In that case, if necessary, a refrigerating machine oil that is more excellent in terms of an action of improving miscibility with the refrigerant, stability of the refrigerant, and the like may be appropriately selected. Although not particularly limited, the stability of the refrigerant can be evaluated by a commonly used method. As an example of such a method, a method of evaluating the amount of free fluorine ions as an index according to ASHRE standard 97-2007. Etc. In addition, the method of evaluating by using the total acid number as an index is also included. This method can be performed, for example, according to ASTM D 974-06.

本発明の組成物は、冷凍機油として、特に限定されないが、例えば、ポリアルキレングリコール（本明細書において、「PAG」と表記することがある。）、ポリオールエステル（本明細書において、「POE」と表記することがある。）及びポリビニルエーテル（明細書において、「PVE」と表記することがある。）からなる群より選択される少なくとも一種を含有していてもよい。   The composition of the present invention is not particularly limited as a refrigerating machine oil, and examples thereof include polyalkylene glycol (sometimes referred to as “PAG” in this specification), polyol ester (herein referred to as “POE”). And at least one selected from the group consisting of polyvinyl ether (in the specification, sometimes referred to as “PVE”).

冷凍機油は、特に限定されないが、40℃における動粘度が5〜400cStであるものを用いることができる。動粘度がこの範囲内にあると、潤滑の点で好ましい。   The refrigerating machine oil is not particularly limited, and one having a kinematic viscosity at 40 ° C. of 5 to 400 cSt can be used. A kinematic viscosity within this range is preferable in terms of lubrication.

上記の場合、冷凍機油の組成物全体に占める割合は、特に限定されないが、通常、10重量%〜50重量%である。   In the above case, the ratio of the refrigerating machine oil to the entire composition is not particularly limited, but is usually 10% by weight to 50% by weight.

本発明の組成物は、特に必須ではないが、例えば過酷な使用条件において高度の安定性が要求される場合等には、必要に応じて安定剤を含有していてもよい。   The composition of the present invention is not particularly essential, but may contain a stabilizer as necessary, for example, when high stability is required under severe use conditions.

この様な安定剤としては、（i）ニトロメタン、ニトロエタン等の脂肪族ニトロ化合物、ニトロベンゼン、ニトロスチレン等の芳香族ニトロ化合物、（ii）１，４−ジオキサン等のエーテル類、2,2,3,3,3−ペンタフルオロプロピルアミン、ジフェニルアミン等のアミン類、ブチルヒドロキシキシレン、ベンゾトリアゾール等が挙げられる。本発明の組成物は、これらの安定剤を、単独で、あるいは２種以上を組み合わせて含有していてもよい。   Such stabilizers include (i) aliphatic nitro compounds such as nitromethane and nitroethane, aromatic nitro compounds such as nitrobenzene and nitrostyrene, (ii) ethers such as 1,4-dioxane, 2,2,3 1,3,3-pentafluoropropylamine, amines such as diphenylamine, butylhydroxyxylene, benzotriazole and the like. The composition of the present invention may contain these stabilizers alone or in combination of two or more.

安定剤の含有量は、安定剤の種類により異なるが、本発明の主要な効果を妨げない範囲で適宜設定できる。安定剤の含有量は冷媒の総量100重量部に対して、通常0.01〜5重量部程度とすることが好ましく、0.05〜2重量部程度とすることがより好ましい。   The content of the stabilizer varies depending on the type of the stabilizer, but can be appropriately set within a range that does not hinder the main effects of the present invention. The content of the stabilizer is usually preferably about 0.01 to 5 parts by weight and more preferably about 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the refrigerant.

本発明の組成物は、必要に応じてさらに重合禁止剤を含んでいてもよい。重合禁止剤としては、特に限定されないが、例えば、4-メトキシ-1-ナフトール、ヒドロキノン、ヒドロキノンメチルエーテル、ジメチル-ｔ-ブチルフェノール、2，6-ジ-tert-ブチル-p-クレゾール、ベンゾトリアゾール等が挙げられる。   The composition of the present invention may further contain a polymerization inhibitor as necessary. The polymerization inhibitor is not particularly limited. For example, 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, benzotriazole, etc. Is mentioned.

重合禁止剤の含有量は冷媒の総量100重量部に対して、通常0.01〜5重量部程度とすることが好ましく、0.05〜2重量部程度とすることがより好ましい。   The content of the polymerization inhibitor is usually preferably about 0.01 to 5 parts by weight and more preferably about 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the refrigerant.

本発明の組成物は、必要に応じてさらに乾燥剤を含んでいてもよい。   The composition of the present invention may further contain a desiccant as required.

本発明の組成物は、必要に応じてさらに他の成分を含んでいてもよい。   The composition of the present invention may further contain other components as necessary.

２．組成物の用途・使用（use）
本発明の組成物は、種々の冷凍機（refrigerator）において使用することができる。なお、本明細書において冷凍機（refrigerator）とは、広義には、物あるいは空間の熱を奪い去ることにより、周囲の外気よりも低い温度にし、かつこの低温を維持する装置全般のことをいう。言い換えれば、広義には、冷凍機は温度の低い方から高い方へ熱を移動させるために、外部からエネルギーを得て仕事を行いエネルギー変換する変換装置のことをいう。本発明において、広義には、冷凍機はヒートポンプと同義である。 2. Use / use of the composition
The composition of the present invention can be used in various refrigerators. In this specification, a refrigerator means a general apparatus that lowers the temperature of the surrounding air by taking away the heat of an object or space and maintains this low temperature. . In other words, in a broad sense, a refrigerator refers to a conversion device that obtains energy from the outside and performs work to convert energy in order to transfer heat from a lower temperature to a higher temperature. In the present invention, a refrigerator is synonymous with a heat pump in a broad sense.

また、本発明において、狭義には、利用する温度領域及び作動温度の違いにより冷凍機はヒートポンプとは区別して用いられる。この場合、大気温度よりも低い温度領域に低温熱源を置くものを冷凍機といい、これに対して低温熱源を大気温度の近くに置いて冷凍サイクルを駆動することによる放熱作用を利用するものをヒートポンプということもある。なお、「冷房モード」及び「暖房モード」等を有するエアコン等のように、同一の機器であるにもかかわらず、狭義の冷凍機及び狭義のヒートポンプの機能を兼ね備えるものも存在する。本明細書においては、特に断りのない限り、「冷凍機」及び「ヒートポンプ」は全て広義の意味で用いられる。   In the present invention, in a narrow sense, the refrigerator is used separately from the heat pump due to the difference in the temperature range to be used and the operating temperature. In this case, a refrigerator that places a low-temperature heat source in a temperature range lower than the atmospheric temperature is called a refrigerator, and on the other hand, a refrigerator that uses a heat dissipation action by driving a refrigeration cycle with a low-temperature heat source placed near the atmospheric temperature. Sometimes called a heat pump. Some air conditioners having the “cooling mode” and the “heating mode” have the functions of a refrigerator in a narrow sense and a heat pump in a narrow sense even though they are the same device. In this specification, unless otherwise specified, “refrigerator” and “heat pump” are all used in a broad sense.

本発明において冷凍機には、特に限定されないが、例えば、冷水機、大型チラー冷凍機（ターボ冷凍機、チラー（チリングユニット）及びスクリュー冷凍機等）、冷凍冷蔵ユニット、冷蔵ショーケース、冷凍ショーケース並びにパッケージエアコン等が含まれる。   In the present invention, the refrigerator is not particularly limited. For example, a refrigerator, a large chiller refrigerator (such as a turbo refrigerator, a chiller (chilling unit), and a screw refrigerator), a refrigerator refrigerator unit, a refrigerator showcase, and a refrigerator showcase. As well as packaged air conditioners.

本発明において、用語「チラー（又はチラー冷凍機）」は、冷媒を収容した冷凍機、並びに水又は不凍液等を循環させる回路を含み、冷却器を通して熱交換を行うシステムを指す。また、用語「大型チラー冷凍機」は、チラーの一種であって、建物単位での空調を目的とした大型空調機を指す。   In the present invention, the term “chiller (or chiller refrigerator)” refers to a system that performs heat exchange through a cooler, including a refrigerator that contains a refrigerant and a circuit that circulates water or antifreeze. The term “large chiller refrigerator” is a kind of chiller and refers to a large air conditioner for air conditioning in units of buildings.

また、本発明において、用語「ターボ冷凍機」は、大型チラー冷凍機の一種であって、蒸発器にて液体の冷媒に熱交換を行わせ、蒸発した冷媒ガスを遠心式圧縮機が吸い込み、断熱圧縮された冷媒ガスを凝縮器で冷却して液化させ、さらに膨張弁を通過させて断熱膨張させた後、蒸発機に再び液体の冷媒として供給する冷凍サイクルからなる冷凍機を指す。   Further, in the present invention, the term “turbo refrigerator” is a kind of large chiller refrigerator, in which heat is exchanged with a liquid refrigerant in an evaporator, and a centrifugal compressor sucks evaporated refrigerant gas, It refers to a refrigerator comprising a refrigeration cycle in which adiabatic-compressed refrigerant gas is cooled and liquefied by a condenser, and further passed through an expansion valve to be adiabatically expanded and then supplied to the evaporator again as a liquid refrigerant.

冷凍機としては、特に限定されないが、蒸気圧縮冷凍機、蒸気噴射冷凍機及び空気サイクル冷凍機等が幅広く挙げられる。代表的なものとして、蒸気圧縮冷凍機が挙げられる。   Although it does not specifically limit as a refrigerator, A vapor compression refrigerator, a steam injection refrigerator, an air cycle refrigerator, etc. are mentioned widely. A typical example is a vapor compression refrigerator.

本発明の組成物を使用できる冷凍機は業務用（工業用、実験用及び運送用等を含む）に好ましく用いられる。   A refrigerator that can use the composition of the present invention is preferably used for business purposes (including industrial, experimental, and transportation purposes).

低圧冷媒は、大型の（チラー）冷凍機に大容量の冷媒を搭載して比較的広い空間の空調を行うために好ましく用いられる。   The low-pressure refrigerant is preferably used for air conditioning in a relatively wide space by mounting a large-capacity refrigerant in a large (chiller) refrigerator.

本発明の組成物は、特に、大型チラー冷凍機用低圧冷媒としての使用に特に適している。   The composition of the present invention is particularly suitable for use as a low-pressure refrigerant for a large chiller refrigerator.

本発明の組成物は、HCFC123の代替冷媒として用いることができる。   The composition of the present invention can be used as an alternative refrigerant for HCFC123.

具体的には、HCFC123を用いて冷凍サイクルを運転する工程を含む冷凍方法において、HCFC123の代わりに本発明の組成物を用いることができる。   Specifically, in the refrigeration method including a step of operating a refrigeration cycle using HCFC123, the composition of the present invention can be used instead of HCFC123.

本発明の組成物はHCFC123と特性が類似しているため、HCFC123が使用されている冷凍空調機器において、本発明の組成物を、HCFC123のドロップイン型代替冷媒又はニアリードロップイン（nearly drop-in）型代替冷媒として用いることができる。   Since the composition of the present invention has characteristics similar to those of HCFC123, the composition of the present invention can be used as a drop-in alternative refrigerant or a nearly drop-in of HCFC123 in a refrigeration and air-conditioning apparatus in which HCFC123 is used. ) Type alternative refrigerant.

３．冷凍方法
本発明の冷凍方法は、本発明の組成物を用いて冷凍サイクルを運転する工程を含む、方法である。 3. Refrigeration method The refrigeration method of the present invention is a method including a step of operating a refrigeration cycle using the composition of the present invention.

冷凍サイクルとしては、主に蒸気圧縮式、蒸気噴射式及び吸収式等が挙げられる。本発明の組成物は、特に限定されないが、蒸気圧縮式冷凍サイクルにおける用途に適している。   The refrigeration cycle mainly includes a vapor compression type, a vapor injection type, an absorption type and the like. The composition of the present invention is not particularly limited, but is suitable for use in a vapor compression refrigeration cycle.

蒸気圧縮式冷凍サイクルとは、冷媒を、（１）気体状態で圧縮機で圧縮し、（２）凝縮器で冷却して圧力が高い液体状態に変え、（３）膨張弁で圧力を下げ、さらに（４）蒸発器において低温で気化させて気化熱により熱を奪い取る、という一連のサイクルからなる。気体状態の冷媒を圧縮する方式によりターボ（遠心式）、レシプロ、ツインスクリュー、シングルスクリュー及びスクロール圧縮機等に分類することができ、熱容量、圧縮比及び大きさにより選択することができる。本発明の組成物は、特に限定されないが、大型チラー冷凍機、特にターボ（遠心式）圧縮機に用いられる冷媒に適している。   The vapor compression refrigeration cycle means that (1) the refrigerant is compressed by a compressor in a gaseous state, (2) is cooled by a condenser to be changed to a high pressure liquid state, (3) the pressure is reduced by an expansion valve, Furthermore, (4) it consists of a series of cycles in which vaporization is performed at a low temperature in an evaporator and heat is taken away by heat of vaporization. It can be classified into turbo (centrifugal), reciprocating, twin screw, single screw, scroll compressor, etc. according to the method of compressing the refrigerant in the gaseous state, and can be selected according to the heat capacity, compression ratio and size. The composition of the present invention is not particularly limited, but is suitable for refrigerants used in large chiller refrigerators, particularly turbo (centrifugal) compressors.

以下、実施例を用いて本発明を説明するが、本発明は何らこれらに限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these at all.

表１に示す本発明の組成物（実施例１〜４）を冷却システム（単段蒸気圧縮式冷媒サイクル）において作動流体として使用した。また、表１に示す比較例１〜６についても同じ冷却システムで同様に使用した。   The compositions (Examples 1 to 4) of the present invention shown in Table 1 were used as working fluids in a cooling system (single-stage vapor compression refrigerant cycle). Further, Comparative Examples 1 to 6 shown in Table 1 were similarly used in the same cooling system.

システムの運転条件は、凝縮器温度；５℃、蒸発器温度；４５℃、過加熱度；２Ｋ、過冷却度；８Ｋとした。   The operating conditions of the system were condenser temperature: 5 ° C., evaporator temperature: 45 ° C., degree of superheating: 2K, degree of supercooling: 8K.

各実施例及び各比較例において、ＣＯＰ及び冷凍能力（ｋＪ／ｍ３）及びガス密度値を測定した。HCFC123、HCFO1233zd(E)及びHFC245faの中で最も冷凍能力が優れているHFC245fa単独の値を１００とした場合の相対値を表２に示す。 In each Example and each Comparative Example, COP, refrigeration capacity (kJ / m 3 ), and gas density value were measured. Table 2 shows the relative values when the value of HFC245fa alone having the highest refrigerating capacity among HCFC123, HCFO1233zd (E) and HFC245fa is 100.

Figure 2015196702
Figure 2015196702

Figure 2015196702
Figure 2015196702

その結果、HCFO123zd(E)とHFC245faとの混合物においては、実施例１〜４に示される組成範囲、すなわちHCFO1233zd(E)/HFC245fa＝18〜49/51〜82mass%で、ＣＯＰがほぼHCFC123を単一冷媒として使用したときと同等であり、かつ冷凍能力及びガス密度がHCFC123、HCFO1233zd(E)又はHFC245faのいずれを単一冷媒として使用したときよりも優れていることが判る。   As a result, in the mixture of HCFO123zd (E) and HFC245fa, the composition range shown in Examples 1 to 4, that is, HCFO1233zd (E) / HFC245fa = 18 to 49/51 to 82 mass%, and COP is almost equal to HCFC123. It can be seen that it is equivalent to the case where it is used as one refrigerant, and the refrigerating capacity and gas density are superior to those when any one of HCFC123, HCFO1233zd (E) or HFC245fa is used as a single refrigerant.

さらに、各実施例の結果は、比較例２（HCFO1233zd(E)/HFC245fa=60/40mass%）と比較しても冷凍能力及びガス密度の点で優れており、HCFO1233zd(E)及びHFC245faからなる組成物のなかでも、実施例で示されている組成を有する冷媒が特に優れていることが判った。   Furthermore, the results of each example are superior in terms of refrigerating capacity and gas density compared to Comparative Example 2 (HCFO1233zd (E) / HFC245fa = 60/40 mass%), and consist of HCFO1233zd (E) and HFC245fa. Among the compositions, it was found that the refrigerants having the compositions shown in the examples are particularly excellent.

Claims (14)

冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比が、18:82〜49:51である、
組成物。 A composition containing a refrigerant,
The refrigerant contains HCFO1233zd (E) and HFC245fa, and
The mass ratio of HCFO1233zd (E) to HFC245fa is 18:82 to 49:51,
Composition. 冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有し、かつ
HCFO1233zd(E)のHFC245faに対する質量比が、29:71〜38:62である、
組成物。 A composition containing a refrigerant,
The refrigerant contains HCFO1233zd (E) and HFC245fa, and
The mass ratio of HCFO1233zd (E) to HFC245fa is 29:71 to 38:62,
Composition. 冷媒を含有する組成物であって、
冷媒が、HCFO1233zd(E)及びHFC245faを含有する共沸乃至共沸様組成物である、
組成物。 A composition containing a refrigerant,
The refrigerant is an azeotropic or azeotrope-like composition containing HCFO1233zd (E) and HFC245fa,
Composition. さらに冷凍機油を含有する、請求項１〜３のいずれかに記載の組成物。   Furthermore, the composition in any one of Claims 1-3 containing refrigerator oil. 前記冷凍機油が、ポリアルキレングリコール（PAG）、ポリオールエステル（POE）及びポリビニルエーテル（PVE）からなる群より選択される少なくとも一種の冷凍機油である、請求項４に記載の組成物。   The composition according to claim 4, wherein the refrigerating machine oil is at least one refrigerating machine oil selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE). 大型チラー冷凍機用冷媒として用いられる、請求項１〜５のいずれかに記載の組成物。   The composition in any one of Claims 1-5 used as a refrigerant | coolant for large chiller refrigerators. 2,2-ジクロロ-1,1,1-トリフルオロエタン（HCFC123）の代替冷媒として用いられる、請求項１〜６のいずれかに記載の組成物。   The composition according to any one of claims 1 to 6, which is used as an alternative refrigerant for 2,2-dichloro-1,1,1-trifluoroethane (HCFC123). 請求項１〜５のいずれかに記載の組成物の、大型チラー冷凍機用の冷媒としての使用。   Use of the composition according to any one of claims 1 to 5 as a refrigerant for a large chiller refrigerator. 請求項１〜５のいずれかに記載の組成物の、HCFC123の代替冷媒としての使用。   Use of the composition according to any one of claims 1 to 5 as an alternative refrigerant for HCFC123. 請求項１〜５のいずれかに記載の組成物を用いて冷凍サイクルを運転する工程を含む、冷凍方法。   A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to claim 1. 請求項１０に記載の工程を含有する、大型チラー冷凍機の運転方法。   The operation method of a large chiller refrigerator containing the process of Claim 10. 請求項１〜５のいずれかに記載の組成物を含む冷凍機。   A refrigerator comprising the composition according to any one of claims 1 to 5. 大型チラー冷凍機である、請求項１２に記載の冷凍機。   The refrigerator according to claim 12, which is a large chiller refrigerator. HCFO1233zd(E)及びHFC245faを含有する組成物の製造方法であって、
HCFO1233zd(E)のHFC245faに対する質量比が18:82〜49:51となるように、少なくともHCFO1233zd(E)及びHFC245faを混合する工程
を含む製造方法。 A method for producing a composition comprising HCFO1233zd (E) and HFC245fa,
A production method comprising a step of mixing at least HCFO1233zd (E) and HFC245fa so that a mass ratio of HCFO1233zd (E) to HFC245fa is 18:82 to 49:51.
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